Curable compositions, processes for using such compositions to prepare composites and processes for preparing composites having superior surface finish and high fiber consolidation

ABSTRACT

Curable compositions, such as oxazine-based ones, are useful in applications within the aerospace industry, such as for example as a thermosetting resin composition for use as a matrix resin in processes, such as resin transfer molding, vacuum assisted transfer molding, resin film infusion, prepregging and towpregging, where the composites or laminates so prepared have superior surface finish and high fiber consolidation.

BACKGROUND

1. Field

Curable compositions, such as oxazine-based ones, are useful inapplications within the aerospace industry, such as for example as athermosetting resin composition for use as a matrix resin in processes,such as resin transfer molding, vacuum assisted transfer molding, resinfilm infusion, prepregging and towpregging, where the composites orlaminates so prepared have superior surface finish and high fiberconsolidation.

2. Brief Description of Related Technology

Epoxy resins with various hardeners have been used extensively in theaerospace industry, both as adhesives and as matrix resins for use inprepreg assembly with a variety of substrates.

Blends of epoxy resins with other resins are known. See e.g. U.S. Pat.No. 4,607,091 (Schreiber), U.S. Pat. No. 5,021,484 (Schreiber), U.S.Pat. No. 5,200,452 (Schreiber), and U.S. Pat. No. 5,445,911 (Schreiber).These blends appear to be potentially useful in the electronics industryas the epoxy resins can reduce the melt viscosity of oxazines allowingfor the use of higher filler loading while maintaining a processableviscosity. However, epoxy resins oftentimes undesirably increase thetemperature at which oxazines polymerize.

Ternary blends of epoxy resins are also known. See U.S. Pat. No.6,207,786 (Ishida), and S. Rimdusit and H. Ishida, “Development of newclass of electronic packaging materials based on ternary system ofbenzoxazine, epoxy, and phenolic resin,” Polymer, 41, 7941-49 (2000).

Resin transfer molding (“RTM”) is a process by which aresin—conventionally and predominately, epoxy-based resin systems andmaleimide-based systems—is pumped at low viscosities and under pressureinto a closed mold die set containing a preform of dry fabric. The resininfuses into the preform to make a fiber-reinforced composite article.The RTM process can be used to produce at low cost composite parts thatare complex in shape. These parts typically require continuous fiberreinforcement along with inside mold line and outside mold linecontrolled surfaces.

Fiber-reinforced composite articles may be manufactured from vacuumassisted resin transfer molding (“VaRTM”), like RTM but with an appliedvacuum. VaRTM typically employs an open mold and places the system undera vacuum to assist the resin infusion process.

Resin film infusion (“RFI”), like RTM, infuses a resin into a preformplaced in a mold. Here, however, the resin is in the form of a film,which is placed in the mold together with the preform. U.S. Pat. No.5,902,535 speaks to RFI molds and processes, and is expresslyincorporated herein by reference.

The matrix resin used in the RTM and VaRTM advanced possesses a lowinjection viscosity to allow complete wetting and infusion of thepreform.

U.S. Patent Application Publication No. 2007/0007692 refers to resintransfer molding, vacuum assisted resin transfer molding and resin filminfusion processes, using a heat curable composition having abenzoxazine component.

Notwithstanding the state of the technology, there is a need for newresin systems for advanced processes, particularly a resin system withimproved performance properties.

SUMMARY

A process for producing composite articles in processes, such as RTM,VaRTM, RFI, prepreg and towpreg systems, using a thermosetting resincomposition and an agent capable of expanding volume when exposed toelevated temperature conditions, such as expandable microspheres.

In one aspect an RTM process is provided, steps of which include:

(a) providing a thermosetting resin composition into a closed moldcontaining a preform, each of which optionally with an agent capable ofexpanding volume;

(b) exposing the interior of the mold to a first elevated temperatureand elevated pressure sufficient to wet the preform with thethermosetting resin composition; and

(c) curing the thermosetting resin composition-impregnated preformwithin the mold at a second elevated temperature to form a RTM product.Provided, of course, that an agent capable of expanding volume ispresent in at least one of the fibers or the thermosetting resincomposition.

In another aspect a VaRTM process is provided, steps of which include:

providing a preform into a mold, optionally with an agent capable ofexpanding volume;

providing a thermosetting resin composition into the mold under a firstelevated temperature and under vacuum for a time sufficient to allow thecomposition to wet the preform where the thermosetting resin compositionoptionally includes an agent capable of expanding volume; and exposingthe mold containing the composition wetted-preform to a second elevatedtemperature while under vacuum sufficient to cure the thermosettingresin composition-wetted preform within the mold to form a VaRTMproduct.

In yet another aspect, there is provided an RFI process, steps of whichinclude:

providing a preform into a closed mold containing a thermosetting resincomposition in film form each of which optionally, with an agent capableof expanding volume;

exposing the interior of the mold to a first elevated temperature andoptionally vacuum, while the exterior of the mold is exposed to anelevated pressure, for a time sufficient to infuse the preform with thethermosetting resin composition; and

curing the thermosetting resin composition-infused preform within themold at a second elevated temperature to form an RFI product. Provided,of course, that an agent capable of expanding volume is present in atleast one of the fibers or the thermosetting resin composition.

In yet another aspect, processes for producing a prepreg are alsoprovided. One such process includes the steps of (a) providing fibers,such as in a layer format, optionally, with an agent capable ofexpanding volume; (b) providing a thermosetting resin composition,optionally with an agent capable of expanding volume; and (c) joiningthe thermosetting resin composition and the fibers to form a prepregassembly, and exposing the resulting prepreg assembly to elevatedtemperature and pressure conditions sufficient to infuse the fibers withthe thermosetting resin composition to form a prepreg.

Another such process for producing a prepreg, includes the steps of (a)providing the fibers, optionally, with an agent capable of expandingvolume; (b) providing the thermosetting resin composition in liquidform, optionally, with; (c) passing the fibers through the liquidthermosetting resin composition to infuse the fibers with thethermosetting resin composition to form a prepreg assembly; and (d)removing excess thermosetting resin composition from the prepregassembly.

In a similar manner to the prepregging processes, towpregging processesare also provided.

In each of these processes, an agent capable of expanding volume, eitherforms part of the thermosetting resin composition, is added to thepreform or fibers, or in the case of RFI, RTM or VaRTM is added in afilm or layer form, or combinations thereof. The agent expands duringthe curing process. This expansion seems to generate an additionalpressure component during the cure process (applied external pressuretogether with pressure from microspheres), leading to a net increase ofthe system “fluid pressure” during cure. This offset at least to adegree the impact of volatile generation during the cure process. Theadditional fluid pressure seems to improve the surface quality of thecomposite laminate, together with and confers upon the laminateincreased mechanical property performance.

In yet another aspect, a film comprising (a) a release liner; (b) aresin component; and (c) an expandable agent, is provided and in yetanother aspect a process for improving the surface finish of and theresin consolidation in a composite or laminate part, steps of whichcomprise (a) providing a perform into a mold; (b) providing such adescribed film onto the perform disposed within the mold; (c) providinga resin into the mold; (d) subjecting the perform, film and resin toconditions appropriate to cure the resin and expand the film to form acomposite or laminate part; and (e) removing the expanded film from thecomposite or laminate part to reveal a composite or laminate part havingimproving surface finish and resin consolidation.

Of course, products made by these processes are also provided.

The present invention will be more fully understood by a reading of thefollowing detailed description of the invention.

DETAILED DESCRIPTION

As noted above, in one aspect a RTM process is provided, steps of whichinclude:

(a) providing a thermosetting resin composition into a closed moldcontaining a preform, each of which optionally, includes or is incontact with an agent capable of expanding volume;

(b) exposing the interior of the mold to a first elevated temperatureand elevated pressure sufficient to wet the preform with thethermosetting resin composition; and

(c) curing the thermosetting resin composition-impregnated preformwithin the mold at a second elevated temperature to form a RTM product.Provided, of course, that an agent capable of expanding volume ispresent in at least one of the fibers or the thermosetting resincomposition.

In another aspect, a VaRTM process is provided, steps of which include:

(a) providing a preform into a mold, where the preform, optionally, isin contact with an agent capable of expanding volume;

(b) providing a thermosetting resin composition into the mold under afirst elevated temperature and under vacuum for a time sufficient toallow the composition to wet the preform, wherein the thermosettingresin composition, optionally, includes an agent capable of expandingvolume; and

(c) exposing the mold containing the composition wetted-preform to asecond elevated temperature while under vacuum sufficient to cure thethermosetting resin composition-wetted preform within the mold to form aVaRTM product.

In yet another aspect, an RFI process is provided, steps of whichinclude:

(a) providing a preform into a closed mold containing a thermosettingresin composition in film form, each of which optionally, with an agentcapable of expanding volume;

(b) exposing the interior of the mold to a first elevated temperatureand optionally vacuum, while the exterior of the mold is exposed to anelevated pressure, for a time sufficient to infuse the preform with thethermosetting resin composition; and

(c) curing the thermosetting resin composition-infused preform withinthe mold at a second elevated temperature to form an RFI product.Provided of course that an agent capable of expanding volume is presentin at least one of the fibers or the thermosetting resin composition.

In certain aspects of these embodiments the agent capable of expandingis presented in a film form. Thus, a film is provided, which broadlyspeaking includes a release liner; b. a resin component; and c. anexpandable agent.

In use, the film can improve the surface finish of and the resinconsolidation in a composite or laminate part. A process for using thefilm therefore includes the steps of:

-   -   a. providing a perform into a mold;    -   b. providing the film onto the perform disposed within the mold;    -   c. providing a resin into the mold;    -   d. subjecting the perform, film and resin to conditions        appropriate to cure the resin and expand the film to form a        composite or laminate part; and    -   e. removing the expanded film from the composite or laminate        part to reveal a composite or laminate part having improving        surface finish and resin consolidation.

In yet another aspect, processes for producing a prepreg are alsoprovided. One such process includes the steps of (a) providing fibers,such as in a layer format, optionally, in contact with an agent capableof expanding volume; (b) providing the thermosetting resin composition,optionally, including an agent capable of expanding volume; and (c)joining the thermosetting resin composition and the fibers to form aprepreg assembly, and exposing the resulting prepreg assembly toelevated temperature and pressure conditions sufficient to infuse thefibers with the thermosetting resin composition to form a prepreg.Provided of course that an agent capable of expanding volume is presentwith or in at least one of the fibers or the thermosetting resincomposition.

Another such process for producing a prepreg, includes the steps of (a)providing the fibers, optionally, with an agent capable of expandingvolume; (b) providing the thermosetting resin composition in liquidform, optionally, with an agent capable of expanding volume; (c) passingthe fibers through the liquid thermosetting resin composition to infusethe fibers with the thermosetting resin composition to form a prepregassembly; and (d) removing excess thermosetting resin composition fromthe prepreg assembly. Again, provided of course that an agent capable ofexpanding volume is present with or in at least one of the fibers or thethermosetting resin composition.

In a similar manner to the prepregging processes, towpregging processesare also provided.

In some of these processes, as noted, an oxazine component, with (ii) anagent capable of expanding volume, either forms part of thethermosetting resin composition or is added to the preform or fibers.

In yet another aspect, a film comprising (a) a release liner; (b) aresin component; and (c) an expandable agent, is provided and in yetanother aspect a process for improving the surface finish of and theresin consolidation in a composite or laminate part, steps of whichcomprise (a) providing a perform into a mold; (b) providing such adescribed film onto the perform disposed within the mold; (c) providinga resin into the mold; (d) subjecting the perform, film and resin toconditions appropriate to cure the resin and expand the film to form acomposite or laminate part; and (e) removing the expanded film from thecomposite or laminate part to reveal a composite or laminate part havingimproving surface finish and resin consolidation.

Of course, the invention provides products, such as RFI, RTM, VaRTM andprepreg or towpreg products, made by these processes.

In still another aspect, the invention provides a bindercomposition—useful in both the RTM and VaRTM processes—which ispartially cured by exposure to elevated temperature conditions over timesufficient to increase the melting point higher than the temperature atwhich a matrix resin composition is to be infused into a preform andlower than the point at which the partially cured binder composition andthe matrix resin composition are miscible.

Complex three dimensional part geometries may be molded in some of theprocesses described herein as a single piece unit. RFI, for instance, isparticularly useful for molding large composite parts, as it defines theentire geometry of the part in a single process cycle, therebyeliminating any subsequent assembly or bonding processes. In theaerospace industry, for one, it is not uncommon for parts to be up to100 feet in length and up to 30 feet in width, located on loftedsurfaces with integral stiffening and attachment details. Using theseprocesses to form such large parts, assembly and tooling costs normallyassociated with a mechanically fastened or bonded structure may bereduced. In addition, narrow engineering tolerances may be realizedusing these advanced processes to enable assembly of a large aircraftstructure with minimal shimming, typically associated withnon-monolithic components constructed from sub-assemblies.

In an RFI process, a resin film molding tool is ordinarily used, whichincludes an outer mold tool, which includes a facing sheet supported bya support structure. A resin film prepared from a thermosetting resincomposition with or without an agent capable of expanding volume forinstance when exposed to elevated temperature conditions, such asexpandable microspheres positioned on the facing sheet, and a preform ispositioned on the resin film. Onto and/or about the preform may also beplaced an agent capable of expanding volume for instance when exposed toelevated temperature conditions, such as expandable microspheres.

The preform is designed in the shape of a desired article to befabricated from compositing materials, such as fibers made from carbon,aramid, ceramic and the like. The preform may include a preform skin, asdescribed in U.S. Pat. No. 5,281,388, the disclosure of which is herebyexpressly incorporated herein by reference.

RTM systems are well known, such as those described in U.S. Pat. Nos.5,369,192, 5,567,499, 5,677,048, 5,851,336, and 6,156,146, which areincorporated herein by reference. VaRTM systems are also well known,such as those described in U.S. Pat. Nos. 5,315,462, 5,480,603 and5,439,635, each of which also expressly are incorporated herein byreference.

RTM systems produce composite articles from resin impregnated preforms.The preform is placed in a cavity mold. Onto and/or about the preformmay also be placed an agent capable of expanding volume for instancewhen exposed to elevated temperature conditions, such as expandablemicrospheres. A thermosetting resin composition is then injected intothe mold to wet and infuse the fibers of the preform. In an RTM process,the thermosetting resin composition is introduced into the cavity moldunder pressure. The thermosetting resin composition-infused preform iscured under elevated temperature. The resulting solid article may besubjected to post curing operations to produce a final compositearticle, though this is not required.

Thus, with the RTM process, the preform is placed, within the mold. Thepreform used in the RTM process may include heat curable bindercomposition, tacked to the fibers which make up the preform.

In an RTM process, therefore, the mold is then closed and thethermosetting resin composition is introduced, and allowed to infuse thepreform. This introduction may occur under mildly elevated temperatureconditions to improve flow characteristics of the thermosetting resincomposition for a time sufficient to allow wetting of the preform.

The interior of the mold is then heated to, and maintained at, atemperature (ordinarily within the range of 250° F. to 350° F.) which issufficient to cure the thermosetting resin composition, for a timesufficient to cure the thermosetting resin composition. This time isordinarily within the 60 to 90 minute range, depending of course on theprecise constituents of the thermosetting resin composition. After cureis complete, the temperature of the mold is allowed to cool and the RTMproduct made by the process is removed.

In a VaRTM process, after providing the preform with or without an agentcapable of expanding volume for instance when exposed to elevatedtemperature conditions, such as expandable microspheres disposed ontoand/or about the preform, a dispersing medium may be disposed thereover.The dispersing medium is positioned on the surface of the prefrom in anenvelope within the mold. The dispersing medium is oftentimes a flexiblesheet or liner. A vacuum is applied to collapse the dispersing mediumagainst the preform and assist in the introduction of the thermosettingresin composition into the mold to wet and infuse the preform. Thethermosetting resin composition may include an agent capable ofexpanding volume for instance when exposed to elevated temperatureconditions, such as expandable microspheres.

The thermosetting resin composition is injected into the mold, andallowed to wet and infuse the preform. This injection may again occurunder a mildly elevated temperature, this time through and under vacuumfor a period of time sufficient to allow the composition to wet andinfuse the preform.

The thermosetting resin composition is introduced under vacuum into theenvelope to wet and infuse the preform. The vacuum is applied to theinterior of the envelope via a vacuum line to collapse the flexiblesheet against the preform. The vacuum draws the thermosetting resincomposition through the preform and helps to avoid the formation of airbubbles or voids in the finished article. The thermosetting resincomposition cures while being subjected to the vacuum.

The mold is then exposed to an elevated temperature, ordinarily withinthe range at 250° F. to 350° F., while remaining under vacuum, for aperiod of time sufficient to cure the thermosetting resincomposition-wetted preform within the mold. This time period again isordinarily within the 60 to 90 minute range. The vacuum also draws offany fumes produced during the curing process. After cure is complete,the temperature of the mold is allowed to cool and the VaRTM productmade by the process is removed.

The resulting solid article so made by the VaRTM process may besubjected to post curing operations to produce a final compositearticle.

The first step in either of the RTM/VaRTM processes is thus to fabricatea fiber preform in the shape of the desired article. The preformgenerally includes a number of fabric layers or plies made from thesefibers that impart the desired reinforcing properties to a resultingcomposite article. Once the fiber preform has been fabricated, thepreform is placed in a mold.

In an alternative embodiment, an agent capable of expanding volume in afilm or layer form may be applied onto the preform disposed within amold, where when the mold is closed and the temperature and/or pressurewithin is elevated positive pressure is provided onto the laminate to beformed from the perform and injected matrix resin such thatconsolidation is enhanced, the effects of cure shrinkage are reduced,cure stress is reduced, surface imperfections and void volume arereduced, and fiber volume and resin/fiber wetting are increased.

Consolidation and cure shrinkage are issues for composite or laminateformation, particularly in RFI, RTM and/or VaRTM processing.Consolidation pressure is ordinarily provided by autoclave or a press,with pressures reaching in the range of up to 100 psi. Even when suchexternal pressure is increased beyond 100 psi, the resin may not seesuch pressure as the fibers begin to bear the load. And resin fluidpressure can further reduce as the resin cures and begins to shrink. Inbuilding a large composite part where a temperature gradient exists atvarious locations within the part, low fluid pressure at and/or duringcure can occur at the temperature lagging areas, resulting in poorwetting and poor composite properties.

In addition, when matrix resins include resins that have low viscosityand high volatility, resin volatilization within the closed mold duringthe infusion process may create imperfection/microvoids in the compositeor laminate.

A layer of an expandable agent—whether applied as a coating in solid orliquid form—should contain an expandable agent at a level of about0.1-100% by weight. The expandable agent should be activated by reachinga certain temperature, which should be from about 25-190° C., at ambientor elevated pressure, which should be in the range of up to about 400psi, such as about 200-400 psi. The expandable agent should be capableof expanding from 1-10,000% of its room temperature volume at theactivation temperature. The form and thickness of the applied layer isadjustable for various mold geometries, with the layer being about 0.02mm or greater in thickness. The matrix of the film layer itself may be athermoplastic or a thermosetting resin film, such as an epoxy orbenzoxazine resin film. When the matrix for the film layer is athermosetting resin it may be based on similar chemistry as the matrixresin described herein. The film may be formed prior to use, and onceformed applied as a layer onto the fiber preform in the closed mold.Alternatively, the film may be formed onto a release substrate, such asa sheet made of Teflon, and the so-formed film applied as a layer ontothe fiber preform in the closed mold.

As noted, in use, the film layer is applied onto the fiber perform,prior to introducing the resin into the closed mold. During cure in aclosed mold process, such as RTM, the film layer expands and exertspositive pressure onto the resin typically before the resin reachesgelation, as the activation temperature of the expandable layer istypically below the temperature at which the resin begins to gel. Thus,a positive fluid pressure is maintained in the resin throughout thegelation thereof. After the processing and the composite or laminate isformed, the film layer itself can be removed, such as by peeling it awayfrom the formed composite or laminate, and thus does not become a partof the formed composite or laminate.

Prepregs formed from fibers, which may be laid up in a layer format, andinfused with the thermosetting resin composition are also provided.

In this regard, processes for producing a prepreg are also provided. Onesuch process includes the steps of (a) providing fibers, such as in alayer format, optionally, with an agent capable of expanding volume; (b)providing the thermosetting resin composition, optionally, with an agentcapable of expanding volume; and (c) joining the thermosetting resincomposition and the fibers to form a prepreg assembly, and exposing theresulting prepreg assembly to elevated temperature and pressureconditions sufficient to infuse the fibers with the thermosetting resincomposition to form a prepreg. Provided of course that an agent capableof expanding volume is present in at least one of the fibers or thethermosetting resin composition.

Another such process for producing a prepreg, includes the steps of (a)providing the fibers, optionally, with an agent capable of expandingvolume; (b) providing the thermosetting resin composition in liquidform, optionally, with an agent capable of expanding volume; (c) passingthe fibers through the liquid thermosetting resin composition to infusethe fibers with the thermosetting resin composition to form a prepregassembly; and (d) removing excess thermosetting resin composition fromthe prepreg assembly. Again, provided of course that an agent capable ofexpanding volume is present in at least one of the fibers or thethermosetting resin composition.

The fiber may be constructed from unidirectional fibers, woven fibers,chopped fibers, non-woven fibers or long, discontinuous fibers.

The fiber chosen may be selected from carbon, glass, aramid, boron,polyalkylene, quartz, polybenzimidazole, polyetheretherketone,polyphenylene sulfide, poly p-phenylene benzobisoxazole, siliconcarbide, phenolformaldehyde, phthalate and napthenoate.

The carbon is selected from polyacrylonitrile, pitch and acrylic, andthe glass is selected from S glass, S2 glass, E glass, R glass, A glass,AR glass, C glass, D glass, ECR glass, glass filament, staple glass, Tglass and zirconium oxide glass.

The preform may be constructed from the same list of materials of whichthe fibers may be constructed.

The thermosetting resin composition should have a viscosity in the rangeof 10 to 5000 cps at resin injection temperature from 160° F. to 250° F.(10 to 3000 cps for RTM or VaRTM; 10-5000 cps for RFI; 1000 to 20000 cpsat an impregnation temperature of 160° F. to 250° F. for matrix resin inprepreg or towpreg). In addition, the time within which the viscosity ofthe thermosetting resin composition increases by 100% under the processconditions is in the range of 30 minutes to 10 hours.

The thermosetting resin composition may include oxazine, oxazoline,epoxy, episulfide, cyanate ester, maleimide, nadimide, itaconimide,phenolic, thiophenolic and combinations thereof.

Where the thermosetting resin composition includes as at least a portionthereof an oxazine component, the oxazine component may be embraced bythe following structure:

where o is 1-4, X is selected from a direct bond (when o is 2), alkyl(when o is 1), alkylene (when o is 2-4), carbonyl (when o is 2), thiol(when o is 1), thioether (when o is 2), sulfoxide (when o is 2), andsulfone (when o is 2), and R₁ is selected from hydrogen, alkyl and aryl.

More specifically, the oxazine may be embraced by the followingstructure:

where X is selected from of a direct bond, CH₂, C(CH₃)₂, C═O, S, S═O andO═S═O, and R₁ and R₂ are the same or different and are selected fromhydrogen, alkyl, such as methyl, ethyl, propyls and butyls, and aryl.

The oxazine thus may be selected from any of the following exemplifiedstructures:

where R₁ and R₂ are as defined above.

Though not embraced by either of oxazine structures I or II additionaloxazines may be embraced by the following structures:

where R₁ are R₂ are as defined above, and R₃ is defined as R₁ or R₂.

Specific examples of these oxazines therefore include:

The oxazine component may include the combination of multifunctionaloxazines and monofunctional oxazines.

Examples of monofunctional oxazines may be embraced by the followingstructure:

where R is alkyl, such as methyl, ethyl, propyls and butyls.

As the oxazoline, compounds embraced by the following structure aresuitable,

where R¹, R², R³, R⁴, and X are hydrogen or as regards x a direct bondto a divalent organic radical, and m is 1.

Exemplary compounds have the structure

in which k is 0-6; m and n are each independently 1 or 2 provided thatat least one of m or n is 1; X is a monovalent or polyvalent radicalselected from branched chain alkyl, alkylene, alkylene oxide, ester,amide, carbamate and urethane species or linkages, having from about 12to about 500 carbon atoms; and R¹ to R⁸ are each independently selectedfrom C₁₋₄₀ alkyl, C₂₋₄₀ alkenyl, each of which being optionallysubstituted or interrupted by one or more —O—, —NH—, —S—, —CO—, —C(O)O—,—NHC(O)—, and C₆₋₂₀ aryl groups.

The oxazoline compounds include 4,4′,5,5′-tetrahydro-2,2′-bis-oxazole,2,2′-bis(2-oxazoline); a 2,2′-(alkanediyl)bis[4,4-dihydrooxazole], e.g.,2,2′-(2,4-butanediyl)bis[4,5-dihydrooxazole] and2,2′-(1,2-ethanediyl)bis[4,5-dihydrooxazole]; a2,2′-(arylene)bis[4,5-dihydrooxazole]; e.g.2,2′-(1,4-phenylene)bis(4,5-dihydrooxazole],2,2′-(1,5-naphthalenyl)bis(4,5-dihydrooxazole],2,2′-(1,3-phenylene)bis[4,5-dihydrooxazole), and2,2′-(1,8-anthracenyl)bis[4,5-dihydrooxazole; a sulfonyl, oxy, thio oralkylene bis 2-(arylene) [4,5-dihydrooxazole, e.g. sulfonyl bis2-(1,4-phenylene) [4,5-dihydrooxazole], thio bis 2,2′-(l, 4-phenylene)[4,5-dihydrooxazole] and methylene bis 2,2′-(1,4-phenylene)[4,5-dihydrooxazole]; a 2,2′,2″-(1,3,5-arylene)tris[4,5-dihydrooxazole],e.g., 2,2′,2″-tris(4,5-dihydrooxazole]1,3,5-benzene; a poly[(2-alkenyl)4,5-hydrooxazole], e.g., poly[2-(2-propenyl)4,5-dihydrooxazole], andothers and mixtures thereof.

In some embodiments, the oxazoline compounds will have the followingstructures.

In general, a large number of polyepoxides having at least about two1,2-epoxy groups per molecule are suitable for use herein. Thepolyepoxides may be saturated, unsaturated, cyclic or acyclic,alipha-tic, alicyclic, aromatic or heterocyclic polyepoxide compounds.Examples of suitable polyepoxides include the polyglycidyl ethers, whichare prepared by reaction of epichlorohydrin or epibromohydrin with apolyphenol in the presence of alkali. Suitable polyphenols therefor are,for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A(bis(4-hydroxyphenyl)-2,2-propane), bisphenol F(bis(4-hydroxyphenyl)-methane), bisphenol S, biphenol,bis(4-hydroxyphenyl)-1,1-isobutane, 4,4′-dihydroxy-benzophenone,bis(4-hydroxyphenyl)-1,1-ethane, and 1,5-hydroxy-naphthalene. Othersuitable polyphenols as the basis for the polyglycidyl ethers are theknown condensation products of phenol and formaldehyde or acetaldehydeof the novolak resin-type.

Other polyepoxides that are in principle suitable for use herein are thepolyglycidyl ethers of polyalcohols or diamines. Such polyglycidylethers are derived from polyalcohols, such as ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,4-butylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediolor trimethylolpropane.

Still other polyepoxides are polyglycidyl esters of polycarboxylicacids, for example, reaction products of glycidol or epichlorohydrinwith aliphatic or aromatic polycarboxylic acids, such as oxalic acid,succinic acid, glutaric acid, terephthalic acid or a dimeric fatty acid.

And still other epoxides are derived from the epoxidation products ofolefinically-unsaturated cycloaliphatic compounds or from natural oilsand fats.

Particularly desirable are liquid epoxy resins derived from the reactionof bisphenol A or bisphenol F and epichlorohydrin. The epoxy resins thatare liquid at room temperature generally have epoxy equivalent weightsof from 150 to about 480.

Typically, the thermosetting resin composition may contain from about 25to about 55 weight percent, such as from about 30 to about 50 weightpercent of epoxy.

The composition may include as at least a portion of the epoxy componenta reactive diluent such as a mono-epoxide (e.g., monoglycidyl ethers ofalkyl- and alkenyl-substituted phenols).

In addition to epoxy, episulfide is desirable as well, whether they arefull or partial episulfides, provided that they are in the solid state.Episulfides may be commercially available or readily prepared from thecorresponding epoxy through known synthetic methods.

The resin component may also include one or more of cyanate ester,maleimide, nadimide, itaconimide, phenolic and/or thiophenolic.

The resin component should be present in the thermosetting resincomposition in an amount in the range of about 5 to about 60 percent byweight, such as about 10 to about 50 percent by weight, desirably about15 to about 35 percent by weight, based on the total weight of thecomposition.

In one version, the thermosetting resin composition may also include atoughener. One such toughener is an acrylonitrile-butadiene co-polymerhaving secondary amine terminal groups. Other tougheners may includepoly(propylene) oxide; polyether sulfone, such as PES 5003P, availablecommercially from Sumitomo Chemical Company, Japan; carboxy-terminatedacrylonitrile butadienes; hydroxy-terminated acrylonitrile butadienes;core shell polymers; and BLENDEX 338, SILTEM STM 1500 and ULTEM 2000,which are available commercially from General Electric Company. ULTEM2000 (CAS Reg. No. 61128-46-9) is a polyetherimide having a molecularweight (“Mw”) of about 30,000±10,000. Those available commercially fromZeon Chemicals under the tradename NIPOL are also desirable. Of theNIPOL branded rubbers, acrylonitrile polybutadiene rubbers areparticularly desirable.

When used, the toughener component should be present in thethermosetting resin component in an amount in the range of about 1 toabout 90 percent by weight, such as about 10 to about 70 percent byweight, desirably about 15 to about 30 percent by weight, based on thetotal weight of the composition.

The curing agent may be selected from nitrogen-containing compounds suchas amine compounds, amide compounds, imidazole compounds, guanidinecompounds, urea compounds and derivatives and combinations thereof.

For instance, the amine compounds may be selected from, aliphaticpolyamines, aromatic polyamines, alicyclic polyamines and combinationsthereof.

The amine compounds may be selected from diethylenetriamine,triethylenetetramine, diethylaminopropylamine, xylenediamine,diaminodiphenylamine, isophoronediamine, menthenediamine andcombinations thereof.

In addition, modified amine compounds, may be used, which include epoxyamine additives formed by the addition of an amine compound to an epoxycompound, for instance, novolac-type resin modified through reactionwith aliphatic amines.

The imidazole compounds may be selected from imidazole, isoimidazole,alkyl-substituted imidazoles, and combinations thereof. Morespecifically, the imidazole compounds are selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole,butylimidazole, 2-heptadecenyl-4-methylimidazole, 2-undecenylimidazole,1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole,1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole,1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,1-guanaminoethyl-2-methylimidazole and addition products of an imidazoleand trimellitic acid, 2-n-heptadecyl-4-methylimidazole, aryl-substitutedimidazoles, phenylimidazole, benzylimidazole,2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole,2-styrylimidazole, 1-(dodecyl benzyl)-2-methylimidazole,2-(2-hydroxyl-4-t-butylphenyl)-4,5-diphenylimidazole,2-(2-methoxyphenyl)-4,5-diphenylimidazole,2-(3-hydroxyphenyl)-4,5-diphenylimidazole,2-(p-dimethylaminophenyl)-4,5-diphenylimidazole,2-(2-hydroxyphenyl)-4,5-diphenylimidazole,di(4,5-diphenyl-2-imidazole)-benzene-1,4,2-naphthyl-4,5-diphenylimidazole,1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, and combinationsthereof.

Modified imidazole compounds may be used as well, which includeimidazole adducts formed by the addition of an imidazole compound to anepoxy compound.

Guanidines, substituted guanidines, substituted ureas, melamine resins,guanamine derivatives, cyclic tertiary amines, aromatic amines and/ormixtures thereof. The hardeners may be involved stoichiometrically inthe hardening reaction; they may, however, also be catalytically active.Examples of substituted guanidines are methyl-guanidine,dimethylguanidine, trimethylguanidine, tetra-methylguanidine,methylisobiguanidine, dimethylisobiguanidine,tetramethyliso-biguanidine, hexamethylisobiguanidine,heptamethylisobiguani-dine and cyanoguani-dine (dicyandiamide).Representative guanamine derivatives include alkylated benzoguan-amineresins, benzoguanamine resins andmethoxymethylethoxy-methylbenzoguanamine.

In addition to or instead of the above-mentioned hardeners,catalytically-active substituted ureas may be used. For instance,p-chlorophenyl-N,N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea(fenuron) or 3,4-dichlorophenyl-N,N-dimethylurea (diuron) arerepresentative examples.

The amount of curing agent may depend upon a number of factors,including whether the curing agent acts as a catalyst or participatesdirectly in crosslinking of the composition, the concentration of epoxygroups and other reactive groups in the composition, the desired curingrate and the like.

The curing agent should be present in an amount in the range of about0.01 to about 40 percent by weight, such as about 0.5 to about 20percent by weight, desirably about 1 to about 15 percent by weight,based on the total weight of the composition.

An agent capable of expanding volume, such as one that undergoes a phasetransition when encountering a chemical stimulus (such as exposure toacidic or basic conditions, for instance) or a physical stimulus like achange in environmental conditions (such as temperature, solvent ormoisture, light, electricity, magnetism, etc.) is also provided.Appropriate agents may include swellable polymers (such as ethylenevinyl alcohol, ethylene vinyl acetate and the like), polyacrylamidegels, shape memory polymers, materials containing Si—H functionality,which can liberate gas hydrogen and azodicarbonamide, a solid blowingagent that decomposes at elevated temperature to liberate a gas(commerically available examples of which are those under the trademarksUNICELL and CELOGEN). As regards azodicarbonamide, the particle size maybe adjusted so as to provide the desired foaming characteristics in thefoamable composition. For example, it has been found that relativelysmall particle size azodicarbonamides tend to produce foams having moreuniform cell structure than coarser grade azodicarbonamides. “Activated”or “modified” forms of azodicarbonamide may be used.

For instance, the agent may be capable of expanding volume when exposedto elevated temperature conditions. The agent may be included as acomponent in the thermosetting resin composition, or contacted with thefibers or preform, or both.

As regards expandable microspheres, U.S. Pat. No. 7,368,167 (Johnston),the disclosure of which is hereby incorporated herein by reference, isdirected to and discloses expandable microspheres, more specificallydry, free-flowing expanded thermoplastic clad microspheres, where thethermoplastic is a polymer material, which functions as a vapor barrierto a blowing agent at the temperatures and pressure differentials ofexpansion of the microsphere, has Tg values of at least about 50° C. anda density of from less than 0.0145 g/cm³ to about 0.005 g/cm³. Whenexposed to elevated temperature conditions, expandable microspheres,rupture to release a blowing agent. See also U.S. Pat. Nos. 5,180,752and 5,580,656, the disclosures of each of which are expresslyincorporated herein by reference. A particularly desirable expandablemicrosphere is manufactured by Henkel Corporation, and is apolyvinylidene chloride-acrylonitrile copolymer or polyacrylonitrilehomopolymer microsphere with an inclusion of iso-butane as the blowingagent.

Microspheres can be made from a rather wide variety of thermoplasticpolymers. In practice, the commercially available microspheres aregenerally limited to polyvinylidene chloride homopolymer or a randomcopolymer of vinylidene chloride and acrylonitrile, or a randomterpolymer of polyvinylidene chloride, acrylonitrile, and divinylbenzene. Microspheres of other materials, such as polyacrylonitrile,polyalkyl methacrylates, polystyrene, or vinyl chloride, are known, butthese materials are not widely and generally available.

Suitable polymers for the formation of thermoplastic microspheres foruse in the present invention include materials which are effective vaporbarriers to the blowing agent at expansion temperatures, and which haveadequate physical properties to form self-supporting expandedmicrospheres with the thin wall thickness attained at the ultra lowdensities produced in the present invention.

Those polymers containing a substantial proportion of acrylic monomerscan be employed whenever the polymer material still functions as a vaporbarrier to the bowing agent at the temperatures and pressuredifferentials of expansion. Preferred polymers are those in which theacrylic monomer, or the majority of the acrylic monomer, isacrylonitrile. The thermoplastic polymers of interest are, for the mostpart, copolymers. Unless otherwise specified, the term copolymer is usedherein in an inclusive sense to connote polymers formed by thepolymerization of two or more monomers, and encompasses terpolymers,tetrapolymers, and the like.

Acrylic monomers useful in forming the thermoplastic polymers in themanufacture of microspheres useful in the present invention includeacrylonitrile, alkyl acrylates and alkyl methacrylates, including methylmethacrylate, methyl acrylate, butyl acrylate, butyl methacrylate,isobutyl methacrylate, stearyl methacrylate, and other related acrylicmonomers such as 1,3-butylene dimethacrylate, allyl methacrylate,trimethylolpropane, trimethacrylate, trimethylolpropane triacrylate,1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, isobornylmethacrylate, dimethylaminoethyl methacrylate, hydroxyethylmethacrylate, hydroxypropyl methacrylate, diurethane dimethacrylate, andethylene glycol dimethacrylate. Other non-acrylic monomers may beincluded in copolymers, styrene, di-vinyl benzene, vinylidene chlorideand the like, typically in minor proportions in the polymer.

A wide variety of blowing agents can be employed in expandablemicrospheres. For instance, lower alkanes, particularly propane, butane,pentane, and mixtures thereof may be used. Blowing agents such as theFreons, such as trichlorofluoromethane, hydrocarbons such as thepentanes or butanes, like n-pentane, i-pentane, neo-pentane, butane,i-butane are commonly found in these types of in situ-expandableparticles. Typically, the unexpanded particles contain from about 3 toabout 40 weight % blowing agent. The selection of the blowing agent is afunction of the particular thermoplastic polymer employed. Isobutene isoften used as the blowing agent with polyvinylidenechloride-acrylonitrile copolymer microspheres.

In unexpanded form, the microspheres can be made in a variety of sizes,those readily available in commerce being most often on the order of 2to 100 μm, particularly 10 to 30 μm. When expanded, these materials willhave bead diameters on the order of about 10 to 300 μm, most commonlyabout 50 to 250 μm, and most often about 100 to 200 μm. Microspheres canbe made from as small as about 0.1 μm, up to as large as about 1millimeter, in diameter, before expansion.

When the microspheres are expanded, they are typically enlarged indiameter by a factor of 7 to 15, and even 20 times the diameter of theunexpanded beads, giving rise to a displacement expanded density, whendry, as low as less than 0.015 g/cm³, preferably less than 0.0145 g/cm³,and down to 0.005 g/cm³.

U.S. Pat. No. 5,397,611 (Wong) reports that the thermoplastic polymerused in forming the in situ-expandable thermoplastic particles arereadily prepared from a wide variety of materials.

Expandable thermoplastic resin microspheres (which can comprise, forexample, volatile physical blowing agents such as hydrocarbons orhalocarbons encapsulated in thermoplastic shells) may also be employedto render the resin foamable. The thermoplastic shells may be comprisedof acrylic-type resins such as polymethylmethacrylate, acrylic-modifiedpolystyrene, polyvinylidene chloride, styrene/MMA copolymers and thelike. Particularly desirable expandable microspheres are available fromAkzo Nobel, NL under the trademark EXPANCEL or from Henkel Corporationunder the trademark DUALITE.

The particle size of the unexpanded particles, as well as the expandedmicrospheres can vary widely. Particle sizes for the unexpandedparticles can range, for example, from about 1 μm to about 1 mm, such asfrom about 2 μm to about 0.5 mm. For instance, DUALITE-brandedexpandable microspheres can range in unexpanded particle size from about5 μm to about 50 μm. The particle diameters expand 2 to 5 times.

Preferably, the particles used have a mixed particle size of wide spreadto achieve the best packing, on expansion, in the syntactic molded foam.A desirable in situ-expandable particle is EXPANCEL 091 DU, which isbelieved to be a terpolymer of vinylidene chloride, acrylonitrile andmethacrylonitrile containing 10-18 weight % isopentane, and possessesthe following properties: average unexpanded particle size of about 12μm with a spread of about 5-50 μm, true density (expanded in water at100° C., kg/m), <20; TMA-T(start)° C., 125-130; T(max)° C., about 183;TMA-density, kg/m³, <17.

When mixed into thermosetting resin compositions the agent capable ofexpanding should be used in an amount of 0.0005% to 5%, such as 0.001%to 10%, like 0.1% to 5%, desirably 0.5% to 1% by weight of the fiberweight. The thermosetting resin composition is then infused into thefiber performs as a liquid or a solid film into the coated dry fiberperforms, under pressure or vacuum into a mold or vacuum bag when thethermosetting resin composition applied to or contacted with the fibersor the preform. The agent can also be applied into a thermosettingmatrix resin (such as one containing an epoxy, a phenolic or abenzoxazine), which is then impregnated into dry fibers tows or fabricsmade with materials such as carbon and glass, to form a prepreg. Or, theagent can be pre-coated onto dry fiber tows or fabrics of materials suchas carbon or glass before impregnation by the thermosetting matrixresin. The agent can also be applied directly onto the surface of theprepregs with the thermosetting matrix resin and fibers or fabrics. Theweight percent of the agent in the prepreg should be in the range from0.001% to 10% by weight of the fiber weight.

The agent as noted may be mixed with the thermosetting resin compositionor applied to or contacted with the fibers or the preform. Theapplication at the fibers or preform may occur by mixing the agent witha carrier vehicle and then spraying the mixture onto the fibers orpreform.

The agent may also be coated onto a preform or into a mold as a separatelayer. As a separate layer onto the preform in a closed mold, the agentprovides positive pressure onto the laminate to enhance consolidation,reduce the effects of cure shrinkage, reduce cure stress, reduceimperfection and void volume, and increase fiber volume and improveresin-fiber wetting. Typically consolidation pressure is provided byautoclave or a press, ordinarily in the range of up to 100 psi. Evenwhen such external pressure is increased beyond 100 psi, the resin maynot see such pressure as the fibers begin to bear the load. And theresin fluid pressure can be further reduced as curing occurs andshrinkage is observed.

In building a large composite part where one or more temperaturegradient(s) exist(s) at various locations within the part, low fluidpressure at cure can occur at the temperature lagging areas, resultingin poor wetting and poor composite properties. In addition, when lowviscosity and high volatile thermosetting resins (such as some liquidbenzoxazines) are used in closed mold infusion, resin volatilizationwithin the mold during the process may create imperfection/micro-voidsin the formed laminate. Using a catalyst to control volatilization mayadversely affect mechanical properties and injection process window.

The expandable layer may be in solid or flowable form, and contains anexpandable agent in an amount of 0.1 up to nearly 100% based on theweight of the layer. The expandable agent in the expandable layer istemperature-activated, and capable of expanding from 1-10000% atactivation temperature, which ordinarily is from 25-190° C. The form andthe thickness of the layer is adjustable to accommodate various moldgeometries. The expandable layer may be applied onto the fiber preform.After the laminate is cured, does not become a part thereof and can beremoved. During cure of the laminate in a closed mold process (such asRTM), the agent in the expandable layer begins to expand (at atemperature below which the thermosetting resin composition starts tocure) and exerts positive pressure onto the resin (typically before theresin reaches gelation). As the activation temperature of the expandablelayer is typically below the temperature at which the resin begins togel, a positive fluid pressure in the resin is maintained throughout thegelation of the resin. In this way, improved laminate fiberconsolidation, fiber volume, fiber wetting, and laminate mechanicalproperties may be realized. The effects of resin cure shrinkage,laminate porosity, and void volume may also be reduced.

In addition, out of autoclave cure (with a vacuum bag pressure or 14.7psi of pressure) may be realized using the invention so describedherein.

In the performance hereof, better fiber consolidation and compaction;better resin and fiber adhesion leading to better mechanicalperformance, such as: impact toughness and interlaminar properties,improved thermal cycling and durability; reduced thermal stress; reducedcure shrinkage; and/or improved surfacing quality, may be observed.

Examples RTM Resin

A resin for use in an RTM process is set forth in the table below, withSample No. 2 representing a resin in accordance with the invention (withexpandable microspheres) and Sample No. 1 representing a control(without expandable microspheres).

Sample No./ Amt. (Wt. %) Component 1 2 Oxazine 74 74 Epoxy Resin 25 24.5Diethylamine salt of 1 1 trifluoromethanesulfonic acid* EXPANCEL 091 DU80 — 0.5 *NACURE SUPER A223

The formulation so formed may be used in a RTM process as follows:

-   -   Preheat the formulation to a temperature of 160° F.    -   Insert a preform into a closed mold    -   Preheat the mold to a temperature of 250° F.    -   Apply vacuum to the mold for a period of time of 1 hour to        remove volatile from the preform    -   Preheat resin injector to a temperature of 235° F.    -   Add the preheated formulation to the injector    -   When the formulation equilibrates at a temperature of 250° F.,        apply full vacuum for a period of time of 15 minutes to remove        air    -   Release the vacuum    -   Inject the formulation at about the rate of 5 to 200 cc per        minute using about 20 psi injection pressure, which may be        increased, if desired throughout the injection to maintain the        desired flow rate    -   When the preform is fully impregnated, close the mold resin exit        ports    -   Pressurize the tool to 100 psi and hold at that pressure for a        period of time of about 10 minutes    -   Ramp the mold temperature to 350° F. at 3° F. per minute    -   When formulation has gelled, remove the applied pressure    -   Hold at a temperature of 350° F. for a period of time of 3 hours    -   Cool to a temperature of 120° F.    -   Open the mold and remove the cured part.

Prepreg Resin

A resin for use in a prepregging process with fiber with the notedcomponents in the specified amount is set forth in the table below.

Sample No./ Amt. (Wt. %) Component 3 4 Oxazine 54 54 Epoxy Resin 18 18Core Shell 5 5 Epoxy-terminated epoxy adduct* 10 10 Diethylamine salt of0.5 0.5 trifluoromethanesulfonic acid EXPANCEL 091 DU 80 — 0.5 Defoamer0.5 — RADEL 105 SFP 12 12 NIPOL 0.3 0.3 *epoxy terminated adduct of twodifferent epoxy materials using bisphenol A as a linking portion.

Products formed by the so-described processes that use agents capable ofexpanding, show improved surface finished and decreased voiding.

For RTM, compression after impact analysis showed CAI of 201 Mpa forSample No. 1 (without expandable microspheres) as compared with 224 forSample No. 2 (with 0.5% expandable microspheres).

For prepreg, compression after impact analysis showed CAI of 253 Mpa forSample No. 3 (without expandable microspheres) as compared with 276 forSample No. 4 (with 0.5% expandable microspheres in the matrix resin). Inaddition, inplane shear strength (“IPS”) of 125 Mpa for Sample No. 3 wasobserved as compared with 134 Mpa for Sample No. 4.

Reduced residual stress of the cured composite (e.g., cured prepreg orRTM) is also seen.

Formation and Use of Film Layer with Expandable Agent

A film layer was made from a composition whose components includebisphenol-A based epoxy resins, epoxy adduct, hydrophobic fumed silica,4,4-diaminodiphenyl sulfone and dicyandiamide, which were blendedtogether and then cast into a film having a thickness of 0.1 mm wasformed with 10% by weight of EXPANCEL 091 DU 80 as an expandable agent.

The film layer so prepared was then coated onto a 0.02 mm thick TEFLONrelease substrate.

The so prepared film (i.e., film layer/release substrate) was appliedonto a dry fiber preform in a closed mold, prior to infusion by the RTMresin—Sample No. 1. And a control run was made without the film. The dryfiber preform consists of 24 plies of dry standard modulus carbonfabrics, plain weave 3K. The RTM process was allowed to proceed, withthe RTM resin infused into the mold and a curing temperature set at 356°F. for a period of time of 2 hours.

The composite or laminate part formed without the film layer resulted ina part having a fiber volume of 55-58% with visually observable surfaceporosity along the edges of the cured composite or laminate part.

In contrast, the composite or laminate part formed with the film whichwas then removed, resulted in a part having a fiber volume of 60%without observable surface porosity along the edges of the curedcomposite or laminate part, or anywhere on the part for that matter.

1. A resin transfer molding process, steps of which comprise: (a)providing a thermosetting resin composition into a closed moldcontaining a preform, optionally with an agent capable of expanding; (b)exposing the interior of the mold to a first elevated temperature andelevated pressure sufficient to wet the preform with the thermosettingresin composition; and (c) curing the thermosetting resincomposition-impregnated preform within the mold at a second elevatedtemperature to form a resin transfer molded product, wherein thethermosetting resin composition comprises (i) a thermosetting resincomprising at least one of epoxy, episulfide, oxazine, oxazoline,cyanate ester, maleimide, nadimide, itaconimide, phenolic andthiophenolic, and wherein at least one of the thermosetting resincomposition or the preform includes the agent capable of expanding. 2.The resin transfer molding process of claim 1, wherein the thermosettingresin composition further comprises (ii) a toughener component. 3.(canceled)
 4. The resin transfer molding process of claim 1, wherein thethermosetting resin composition has a viscosity in the range of 10 to3000 centipoise at the resin injection temperature.
 5. The resintransfer molding process of claim 1, wherein the time within which theviscosity of the thermosetting resin composition increases by 100% underthe process conditions is in the range of 30 minutes to 10 hours at theinjection temperature.
 6. The resin transfer molding process of claim 1wherein the plurality of fabric plies or unidirectional plies comprisesfibers selected from glass, carbon, aramid and ceramics.
 7. The resintransfer molding process of claim 1, wherein the agent capable ofexpanding is a plurality of expandable microspheres.
 8. A resin transfermolded product made by the process of claim 1=4.
 9. A resin transfermolding preform comprising: (a) a plurality of fabric plies orunidirectional plies, (b) a heat curable binder composition, tacked tothe plurality of fabric plies or unidirectional plies, wherein the heatcurable binder composition comprises (i) an oxazine component, and (ii)at least one of epoxy, episulfide, oxazoline, cyanate ester, maleimide,nadimide, itaconimide, phenolic and thiophenolic, and (c) an agentcapable of expanding volume, wherein the agent is present with or in atleast one of (a) or (b), respectively.
 10. The resin transfer moldingpreform of claim 9, wherein the heat curable binder composition furthercomprises optionally, a spacer selected from the group consisting ofparticles constructed of thermoplastics, rubbers, metals, carbon, coreshell, ceramics and combinations thereof.
 11. A vacuum assisted resintransfer molding process, steps of which comprise: (a) providing apreform into a mold, wherein the preform optionally includes an agentcapable of expanding; (b) providing a thermosetting resin compositioninto the mold under a first elevated temperature and under vacuum for atime sufficient to allow the composition to wet the preform, where theresin composition; and (c) exposing the mold containing the compositionwetted-preform to a second elevated temperature while under vacuumsufficient to cure the thermosetting resin composition-wetted preformwithin the mold to form a resin transfer molded product, wherein thethermosetting resin composition comprises (i) an oxazine component and(ii) at least one of epoxy, episulfide, oxazoline, cyanate ester,maleimide, nadimide, itaconimide, phenolic and thiophenolic, and whereinat least one of the preform or the thermosetting resin compositionincludes an agent capable of expanding.
 12. The vacuum assisted resintransfer molding process of claim 11, wherein after providing thepreform a dispersing medium is provided thereover.
 13. The vacuumassisted resin transfer molding process of claim 11, wherein thethermosetting resin composition further comprises (iii) a toughenercomponent.
 14. (canceled)
 15. The vacuum assisted resin transfer moldingprocess of claim 11, wherein the thermosetting resin composition has aviscosity in the range of 10 to 2000 centipoise at transfer moldingtemperature.
 16. The vacuum assisted resin transfer molding process ofclaim 11, wherein the time within which the viscosity of thethermosetting resin composition increases by 100% under the processconditions is in the range of 30 minutes to 10 hours at the resintransfer temperature.
 17. The vacuum assisted resin transfer moldingprocess of claim 11, wherein the preform comprises fibers selected fromglass, carbon, aramid, ceramics and combinations thereof.
 18. A vacuumassisted resin transfer molded product made by the process of claim 11.19. A vacuum assisted resin transfer molding preform comprising: (a) aplurality of fabric plies or unidirectional plies, optionally with anagent capable of expanding and (b) a heat curable binder composition,optionally with an agent capable of expanding, tacked to the pluralityof fabric plies or unidirectional plies, wherein the heat curable bindercomposition comprises (i) an oxazine component and (ii) at least one ofepoxy, episulfide, oxazoline, cyanate ester, maleimide, nadimide,itaconimide, phenolic and thiophenolic, and wherein at least one of theplurality of fabric plies or unidirectional plies or the heat curablebinder composition includes an agent capable of expanding.
 20. Thevacuum assisted resin transfer molding preform of claim 19, wherein theheat curable binder composition further comprises (ii) a toughenercomponent.
 21. (canceled)
 22. The vacuum assisted resin transfer moldingpreform of claim 19, wherein the heat curable binder composition furthercomprises optionally, a spacer selected from the group consisting ofparticles constructed of thermoplastics, rubbers, metals, carbon, coreshell, ceramics and combinations thereof.
 23. The vacuum assisted resintransfer molding preform of claim 19, wherein the plurality of fabricplies or unidirectional plies comprises fibers selected from glass,carbon, aramid, ceramics and combinations thereof.
 24. A resin filminfusion process, steps of which comprise: (a) providing a preform intoa closed mold containing a thermosetting resin composition in film formeach of which is an agent capable of expanding; (b) exposing theinterior of the mold to a first elevated temperature and optionallyvacuum, while the exterior of the mold is exposed to an elevatedpressure, for a time sufficient to infuse the preform with thethermosetting resin composition; and (c) curing the thermosetting resincomposition-infused preform within the mold at a second elevatedtemperature to form a resin transfer molded product, wherein thethermosetting resin composition comprises (i) an oxazine component and(ii) at least one of epoxy, episulfide, oxazoline, cyanate ester,maleimide, nadimide, itaconimide, phenolic and thiophenolic, and whereinat least one of the preform or the thermosetting resin composition infilm form includes an agent capable of expanding.
 25. The resin filminfusion process of claim 24, wherein the thermosetting resincomposition further comprises (iii) a toughener component. 26.(canceled)
 27. The resin film infusion process of claim 24, wherein thethermosetting resin composition has a viscosity in the range of 10 to5000 centipoise at the infusion temperature.
 28. The resin film infusionprocess of claim 24, wherein the time within which the viscosity of thethermosetting resin composition increases by 100% under the processconditions is in the range of 30 minutes to 10 hours at the infusiontemperature.
 29. The resin film infusion process of claim 24, whereinthe preform comprises fibers selected from glass, carbon, aramid,ceramics and combinations thereof.
 30. A resin film infused product madeby the process of claim
 24. 31. A prepreg comprising fibers infused witha thermosetting resin composition, comprising a resin componentcomprising (i) an oxazine component and (ii) at least one of epoxy,episulfide, oxazine, oxazoline, cyanate ester, maleimide, nadimide,itaconimide, phenolic and thiophenolic, at least one of the fibers orthe resin component includes an agent capable of expanding.
 32. Aprepreg process comprising the steps of: providing a plurality offibers; providing a thermosetting resin composition comprising a resincomponent comprising (i) an oxazine component and (ii) at least one ofepoxy, episulfide, oxazoline, cyanate ester, maleimide, nadimide,itaconimide, phenolic and thiophenolic; providing an agent capable ofexpanding wherein at least one of the fibers or the agent capable ofexpanding onto or about the layer of fibers.
 33. The prepreg of claim31, wherein the fibers are oriented in a layer.
 34. The prepreg of claim9, wherein the fiber layer is made from unidirectional fibers.
 35. Theprepreg of claim 9, wherein the fiber layer is made from woven fibers.36. A process for producing a prepreg, steps of which comprise: (a)providing a layer of fibers; (b) providing a thermosetting resincomposition in liquid form; (c) passing the layer of fibers through theliquid thermosetting resin composition to infuse the layer of fiberswith the thermosetting resin composition thereby forming a prepregassembly; and (d) removing excess thermosetting resin composition fromthe prepreg assembly, wherein thermosetting resin composition comprises(i) an oxazine component and (ii) at least one of epoxy, episulfide,oxazoline, cyanate ester, maleimide, nadimide, itaconimide, phenolic andthiophenolic, and wherein at least one of the layer of fibers or thethermosetting resin composition includes an agent capable of expanding.37. The process of claim 36, wherein the prepreg assembly is exposed toelevated temperature and pressure conditions.
 38. A prepreg made by theprocess of claim claim
 32. 39. A prepreg made by the process of claimclaim
 36. 40. Cured reaction product of the prepreg of claim
 38. 41.Cured reaction product of the prepreg of claim
 39. 42. A filmcomprising: a. a release liner; b. a resin component comprising (i) anoxazine component and (ii) at least one of epoxy, episulfide, oxazine,oxazoline, cyanate ester, maleimide, nadimide, itaconimide, phenolic andthiophenolic; and c. an expandable agent.
 43. A process for improvingthe surface finish of and the resin consolidation in a composite orlaminate part, steps of which comprise: a. providing a perform into amold; b. providing a film according to claim 42 onto the performdisposed within the mold; c. providing a resin into the mold; d.subjecting the perform, film and resin to conditions appropriate to curethe resin and expand the film to form a composite or laminate part; ande. removing the expanded film from the composite or laminate part toreveal a composite or laminate part having improving surface finish andresin consolidation.